N-halophenyl derivatives of leucauramine



United States Patent 2,828,341 i OPl E i 1 .T R' YKTWE T 43FLEUCKURAMINE Clyde S. Adams, Yellow Springs, Marjorie J. Cormack,

Dayton, :an'd -Mary lieu Frazierr spriiigfield, Ohio, as-

signors to The Nation'al Cash Register Company, Dayton, Ohio, aicorp'or'ation of Maryland No Drawing. Application November 1, 1955Serial No. 544,376

6 Claims. (Cl. 260-570) This invention relates to the N-halophenylderivatives of "leucauramine having the general structure :"less; whichmay be I used as -color reacta nts because-they :turntoa dark blue 7orggreen blue.color on con ing llltO adsorption contact with acidicsvtypesvof: inorganic-42cmikaolin, beutonite, -alunrinumgsulfate;;zeolitemateri'ahsilica Cgels, magnesium trisilioate, and zinc sulphide,among others, and are useful in solution forxprintingtin eolor on papereoated or-filled -with such adsorbents. Qtherwise, they are very'light-stable and annospherically stable both in their leucauramine formsand in their colored states.

The great utility of these compounds, as at present known, istheirnusejntransfer.cGatings-inmanifOId record systems wherein'the irearsurface of an overlying sheet of record material is coated withafcomposition containing one or more of the noveltleucauraminederivatives and the underlying sheet containing particles of the acidicreactant. In such manifoldisystems the leucauramine derivative isusually dissolved in a suitable solvent and carried as droplets in ahydrophilic colloid film coating on the rear of theovenlyingshee't."'"When the two sheets are in contact and a printed orwritten impression is made on the top surface of the overlying .sheet,rupturingthe film locally so it may be adsorbed by the adidicparticlesin the coating of the under sheet. Such contact will make blue orblue-green marks on the top surface of the under sheet at thepoints-ef'pre'ssure. Such amatiifold system is disclosed in U. S. Patent2,112,507 which issued July 5, 1955, on the application of Barrett K.Green.

The halogenated derivatives of N-phenyl leucauramine are much moresuitable for the manifold systems mentioned than the knownutih'alogenated N-phenyl leucauramine, because they are less volatile,they have increased solubility in oil, and theya're much more stable com2 pounds in the leuco form when subjected to atmospheric conditions andlight.

The leucauramine derivatives also are useful in solid powdered form asone of two solid powdered materials 5 dispersedain aicoating=on"'one"'s'ide bfea record'mater'ial sheetfthe second material beingone of .the acidic inorganic materials-which cause a blue'or"blue .-green color to appear when marked with a stylus. Such a record sheet isdisclosedin U. S. Patent 2,505,470 which issued, on the application ohBarrttKtfir'een-fon April 25, 1950. "a one process of nialcing the novelcompounds consists of the steps of condensing molar equivalents ofMichlers hydrol and a selectediehalogenated aniline in hot ethylalcohol; concentrating :the reaction mixture as far as necessary tocause precipitation on cooling; filtering; purifying the crude materialby treating a benzene solution of it with fullers earth and activatedcharcoal; and then precipitating out the reaction product by theaddition of petroleum ether. The general equation for this reaction isas--. follows:

* 'anesnbstnfitee eneauranime where X is a halo-substituted ianyl'niicleus.

I Leucauramine itself :has :the structure:

(CHa)2N H N( a)2 i The novel derivatives of this'sinventiontnray be considerecl as derivatives of leucauramine-in that one of the hydrogenatomsattached to the (UN has been replaced by a halorsubstitutedphenylegroup.

. As afiist'specifimexarnple bf"the"process, consider the making ofN-(o-chlorophenyl)leucauramiue:

25.6 grams (0.2 rn'olefiof o-chloraniline, and 54.0 grams (0.2 mole) ofMichlers hydrol are dissolved in 200.0 grams oflethyl alcohol in around-bottomed fla'sk, fitted with a water-cooled reflux condenser. Thesolution is refluxed for four hours on a steam bath after'which thesolution is allowed to cool to room temperature. The crystals which haveseparated out are filtered off by suction and. washed with 'sniallamonntsbf-cdld etliyl arsenal, .The filtr'ate ma be concentratedforadditional"cropsofcrystals. i The resultant crude productisdissolve'd in J /ZJitersb'f hot'benjzene, treated with activatedcharcoal, and ifi'illers earth,

andfiilt'ereil. I'Thejfihrate 'is eifaporatedlo 7200, 'i'fiilliliters,vcooled, and; the reaction product precipiarea but with petroleum ether.The resultingpureematerial is a white crystalline substance. Following.is a representation of the reaction:

(CHahN. .0 81001101 7 ahN mom); v i

The m-chlorophenyl and p-chlorophenyl derivatives may be made by usingin place of the o-chloroaniline used in the example, m-chloroaniline orthe p-chloroaniline.

The o-bromop'henyl, m-brornophenyl, and p-bromophenyl derivatives may bemade by using, instead of the chlorinated anilines, the selectedbrominated anilines, using the same relative molecular proportions.

The dichlorophenyl, trichlorophenyl, tetrachlorophenyl, dibromophenyl,tribromophenyl, and tetrabromophenyl derivatives may be made in the samemanner by using the selected halogenated aniline in the same molecularproportions.

As a second specific example, the N-(2,4-dichlorophenyl)leucauramine, isprepared by taking:

32.4 grams (0.2 mole) of 2,4-dichloroaniline, and

54.0 grams (0.2 mole) of Michlers hydrol and dissolving in 200.0 gramsof ethyl alcohol.

The rest of the procedure is identical to that given in the firstspecific example, according to the following and results in a whitecrystalline compound. The other dichloro and dibromo derivatives may beprepared according to the same procedure.

In a similar manner the trichlorophenyl, tribromophenyl,tetrachlorophenyl and tetrabromophenyl derivatives may be made simply bychoosing the selected ha1o-' genated aniline for the reaction using thesame molecular proportions.

Mixed types of N-chloro-bromophenyl derivatives may be made in exactlythe same way by using anilines in which both bromine and chlorine aresubstituted in the same phenyl group.

What is claimed is:

1. The N-halophenyl derivatives of leucauramine, which derivativeshave:the.general structure:

where R is taken from the group consisting of o-halo; m-halo; p-halo;2,3-dihalo; 2,4-dahal0; 2,5-dihalo; 3,4- dihalo; 3,5-dihalo;2,3,4-trihalo; 2,3,5-trihalo; 3,4,5-trihalo; 2,4,5-trihalo; and2,3,4,5tetrahalo, and in which the halo substituent in any position maybe taken from the group consisting of chlorine and bromine.

2. The N-halophenyl derivatives of leucauramine, which derivatives havethe general structure:

( ahN- N( Ha)2 where R is taken fromthe group consisting of o-chloro;o-bromo; m-chloro; m-bromo; p-chloro; p-bromo; 2,3-dichloro;2,3-dibromo; 2,4-dichl0ro; 2,4-dibromo; 2,5-di- 'chloro; 2,5-dibromo;3,4-dichloro; 3,4-dibromo; 3,5-dichloro; 3,5-dibromo; 2,3,4-trich1oro;2,3,4-tribromo; 2,3,5-trichloro; 2,3,5-tribromo; 3,4,5-trich1oro;3,4,5-tribromo; 2,4,5-trichloro; 2,4,5-tribromo; 2,3,4,5-tetrachloro;and 2,3,4,5-tetrabromo.

3. The compound N-(2,5-dichlorophenyl)leucauramine, having thestructure:

(CHa):N N(C a):

4. The compound N-(m-bromophenyl)leucauramine, having the structure:

( ahN N( a)s 5 6 5. The compound N-(m-chlorophenyl)leucauramine, 6. Thecompound N-(2,4-dich10rophenyl)leueaurhaving the structure: amine,having the structure;

H (CHMN H N(C a)x (CHQIN I? N(C I): 5 5 C 1%I-H 1%I-H

1. THE N-HALOPHENYL DERIVATIVES OF LEUCAURAMINE, WHICH DERIVATIVES HAVETHE GENERAL STRUCTURE: